Nordic Polymer Days 2013

Truly Nordic
 Svenska Kemistsamfundets Polymerdagar
1963 organized by Prof. Bengt Rånby
 15 Presentations from Sweden
 2 Presentations from USA
 1 Presentation from Denmark by a graduate
student named Charles M. Hansen
 The “Nordic” requirement, presentations from
at least two Nordic countries, was fulfilled.
UNDERSTANDING ABSORPTION IN POLYMERS:
KEY TO IMPROVING BARRIER PROPERTIES
NORDIC POLYMER DAYS 2013 HELSINKI
Charles M. Hansen, Actively Retired

Mismatch Hansen solubility parameters to get

1. Lower equilibrium absorption, and therefore:
A. Lower concentration gradients
B. Lower diffusion coefficients
C. Lower surface mass transfer coefficients
and
Better Barriers
 The Message is:
The Diffusion Equation is Valid
 1963: Drying of solvent from polymer
 2013: Sorption of solvent by polymer

 Exactly the same equations and data can be

used to satisfactorily model desorption (film
formation) and absorption, as well as
permeation.
 There are no ”Anomalies” in absorption!
 Stress related effects are not (that) signficant
 OUTLINE
 Laws of Diffusion
 Find correct diffusion coefficients

 Concentration dependent coefficients

 Surface condition can be significant

 Combine these to:

1. Model film formation by solvent evaporation

2. Model ”anomalies” of absorption
FICK’S FIRST AND SECOND LAWS

Law 1: F = - D0(c/x)

For mass transport in the x Direction, and

Law 2: c/t = /x (D0c/x)

This is also called the Diffusion Equation.

(Accumulation equals flux in minus flux out)
 DIMENSIONLESS VARIABLES

Dimensionless time:
2 2 2
T = D0t/L (cm /s)(s/cm )
Dimensionless distance:
X = x/L
Dimensionless concentration:
C = (c – c0)/(c - c0)

L is the thickness of a free film

 MEASURING DIFFUSION
COEFFICIENTS
Half-time (t½) equation for measuring D0
2
D0 = 0.049 L /t½
Corrections required for concentration
dependence (M) and surface resistance (B)
See also Nordtest POLY 188
0.049  L2
D(c)  FM  FB
t½
CORRECTIONS FOR CONCENTRATION
DEPENDENCE ALONE
Note huge corrections for desorption
Desorption Absorption
Dmax/D0 (Fd)1/2 (Fd)1/4 (Fa)1/2
1 1.00 1.00 1.00
2 1.56 1.55 1.30
5 2.70 2.61 1.70
101 4.00 3.84 2.01
102 13.40 10.20 3.30
103 43.30 23.10 4.85
104 138.7 47.40 6.14
105 443.0 89.0 7.63
106 1,370.0 160.5 8.97
107 4,300.0 290.0 10.60
108 13,670.0 506.0 12.10
 SURFACE CONDITION
Fs = h(Ceq – Cs) = -DsCs/x

Flux through surface to(from) external phase

equals flux through surface from(to) the bulk.
External Flux to/from surface, Fs, equals mass
transfer coefficient, h, (cm/s) times
3 2
concentration difference, g/cm giving g/cm s
Flux to/from bulk equals diffusion coefficient
2 3
(cm /s) times concentration gradient (g/cm cm)
h can be found from h = Fs /(Ceq – Cs) @ t = 0
CORRECTIONS FOR SURFACE RESISTANCE
FOR D0 = CONST.
B = hL/D0 = Rd/Rs
B 1/B FB
 0 1.0
10 0.1 1.45
2 0.5 3.14
1 1 4.95
0.5 2 6.8
0.1 10 37.5
EXPONENTIAL DIFFUSION COEFFICIENTS FOR
CHLOROBENZENE IN POLY(VINYL ACETATE)
The system chlorobenzene in poly(vinyl acetate)
has been studied extensively with all relevant
data reported in my thesis and subsequent
journal articles. These data give a coherent
understanding of diffusion in polymers including:
Absorption data from one equilibrium to another
Desorption data from different equilibrium values
to vacuum, and film drying (years), but
only
if one accounts for concentration dependence
and significant surface effects when present.
D(c) FOR CHLOROBENZENE IN PVAc FOR
ALL CONCENTRATIONS (HANSEN, 1967)

Isotope Self-
4 technique diffusion
0.2 Vf ~ 1 decade DC
6 Absorption
- LOG D, cm²/sec

D 1 (dry film)
8
0.03 Vf ~ Desorption DAPP
1 decade
10
Absorption

12

14
0 0.2 0.4 0.6 0.8 1.0
Vf
DRYING OF A LACQUER FILM
(Hansen, 1963, 1967, 1968)
10 1
V2 = 10 6
Vt = 10 10
CA = 0·2
B as indicated
Volume Solvent / Volume Polymer

Exptl.
10 165 microns

B=10 6 Exptl. B=10 5

B=10 7 22 microns
~ MO CS = O
CA CA For B=10 5
CS = O
CS = O Calculated
For B=10 7
10 -1 For B=10 6
Experimental

Effect of water - a steeper slope

One day L=30 microns

10 -2
10 -7 10 -6 10 -5 10 -4 10 -3 10 -2
DO t
T, Dimensionsless
(L) 2
 RELATIVE SOLVENT RETENTION
(HANSEN, 1967)
MOLECULAR SIZE AND SHAPE
Cl
H3C CH3
O
+
N
O O H3C O CH3
O
Cl O
O
H3C O CH3 CH3
HC H3C
H3C3 CH3
CH3

OH O H3C
HO
O
O CH3
+
N
CH3 O O
H3C
CH3 CH3
O
O CH3 HO CH3
+ O
N
CH3 CH3 O O O

O
OH
CH3 O HO H3C
O CH3
O
H3C CH3
DESORPTION AND ABSORPTION GIVE SAME
D(c) WITH CORRECTION (HANSEN 1967, 2007)

Isotope
- LOG diffusion coefficient at 20 °C, cm²/sec

8
Absorption F = Fa x FB F = Fa x FB
= 1.3 x 1.25 = 1.2 x 250
Fa = 1.8 = 1.63 = 300
Fd = 144
10

Desorption
(to vacuum)
12
Fd = 40

14
0.1 0.2 0.3 0.4 0.5 0.6
Vf
 ABSORPTION WITH CORRECTIONS
(Fa) REQUIRED FOR D(c) AND FB FOR Rs
Chlorobenzene / polyvinyl acetate

1.0 L = 118 µm
C0 = 0.22 Vf
0.8 C = 0.27 Vf
Mt / M

0.6 Fa ½ = 1.3
D = 1.8(10)-8 cm² FB = 1.25 B ~ 15
sec
0.4 Fa ½ x F B = 1.63

0.2

0
1 2 3 4 5 6 7 8
t , min ½
 Data: Hasimi et al. Eur.Polym.J. 2008;44:4098-4107
ABSORPTION OF WATER VAPOR INTO PVAlc
FROM BONE DRY TO 0.748 VOLUME FRACTION
 POTENTIALLY SIGNIFICANT SURFACE
EFFECTS IN VAPOR ABSORPTION

 External phase diffusion from source to film

 Diffusion in stagnant boundary layer at film
 Heat removal on condensation
 Adsorption (How well do HSP match?)
 Orientation (Does n-hexane enter sideways?)
 Absorption site (hole size and shape)
 Transport into bulk (Diffusion coefficient,
molecular size and shape)
SURFACE RESISTANCE FOR LIQUID CONTACT
®
COC POLYMER TOPAS 6013 TICONA
(NIELSEN, HANSEN 2005)
Absorption of selected solvents in a COC polymer

1200
300

1000
200

800
Weight change in mg/g

100

600
Hexane

0 THF
0 5 10 15 20
400 Diethylether

1,2-Dichloroethylene

200

0
0 20 40 60 80 100 120 140 160
Sqrt time in min
 S-SHAPED CURVES CAUSED BY SURFACE
RESISTANCE (NIELSEN, HANSEN 2005)

Absorption of selected solvents in a COC polymer

60
Weigth change in mg/g

50

40
Butylacetate
30
Ethylacetate
20

10

0
0 50 100 150 200 250 300 350 400
Sqrt time in min
 Apparent h and Equilibrium Uptake for
®
COC Topas 6013 on Liquid Contact
Solvent Apparent h, cm/s Equilibrium uptake, vol. fraction
Tetrahydrofuran 1.89(10)-4 0.676
Hexane 7.78(10)-6 0.351
Diethyl ether 1.21(10)-6 0.268
Propylamine 1.49(10)-7 0.181
Ethylene dichloride 1.18(10)-7 0.176
Ethyl acetate 1.46(10)-8 0.076
n-Butyl acetate 8.30(10)-10 0.202
Phenyl acetate 0 0
Acetophenone 0 0
1,4-Dioxane 0 0
 Tetrahydrofuran apparent h is too low since diffusion controls.

 n-Butyl acetate apparent h is strongly lowered by size and shape.

 ®
Surface Mass Transfer COC (Topas 6013)
Depends On Equilibrium Absorption.
Equilibrium Absorption depends on ΔHSP
Correlation of log(h) with C
-3

-3.5

-4

-4.5

-5
log(h)

-5.5

-6

-6.5

-7

-7.5

-8
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
C (Saturated Vol Fraction)
 MAJOR REFERENCES EXPLAINING
“ANOMALIES” USING DIFFUSION EQUATION
Chapter 16 of Second Edition of Hansen Solubility
Parameters: A User’s Handbook, CRC Press, 2007.
Hansen CM. The significance of the surface condition in
solutions to the diffusion equation: explaining
"anomalous" sigmoidal, Case II, and Super Case II
absorption behavior. Eur Polym J 2010;46;651-662.
Abbott S, Hansen CM, Yamamoto H. Hansen Solubility
Parameters in Practice, www.hansen-solubility.com.
(includes software for absorption, desorption and
permeation)
Downloads on www.hansen-solubility.com. Including this
presentation with comments
Thomas and Windle Case II Example
Methanol/PMMA with Iodine Tracer
Straight line absorption
with linear time cited as
excellent example of
Case II behavior.
This result is duplicated:
Diffusion equation with
significant surface effect
and exponential D(c)
Thomas and Windle Case II Example
Windle, “Case II Sorption” in Comyn, Polymer Permeability (1985)

Iodine tracer lags methanol

in PMMA at 30°C showing
apparent step-like gradient.
Methanol does not have this
“advancing sharp front”.
Iodine tracer is far too slow
as shown in the following.
Methanol gradients become
horizontal, not vertical.
THOMAS AND WINDLE EXPERIMENT
6.3 HOURS
THOMAS AND WINDLE EXPERIMENT
11.3 HOURS
THOMAS AND WINDLE EXPERIMENT
19.3 HOURS
Methanol/PMMA Absorption at 30ºC
Calculated Concentration Gradients Flat at 13 hours
Effect of Molecular Properties on D0
Compare Methanol with Iodine
Super Case II: n-Hexane/Polystyrene
Hopfenberg and Coworkers
Hopfenberg and Coworkers Super Case II
Correctly Modeled Absorption, D0, and h.
 HANSEN IS “EXTRANEOUS”:
PETROPOULOS et.al
Hansen is extraneous; challenges included

Petropoulos JH Sanopoulou M Papadokostaki KG.

Physically insightful modeling of non-Fickian
kinetic energy regimes encountered in
fundamental studies of isothermal sorption of
swelling agents in polymeric media.
Eur Polym J 2011;47:2053-2062.
 Hansen cannot explain these data!
Next two slides do explain these data for liquid
dichloromethane absorption into stretched, confined
Cellulose Acetate
CALCULATED ABSORPTION CURVE AND GRADIENTS
MATCH EXPERIMENTAL DATA FOR ABSORPTION
PERPENDICULAR TO STRETCH DIRECTION:
METHYLENE CHLORIDE IN CELLULOSE ACETATE.
CALCULATED ABSORPTION CURVE IS PERFECT, FRONT
NOT A SHARP STEP, BUT CLOSE TO EXPERIMENTAL.
METHYLENE CHLORIDE IN STRETCH DIRECTION.
ARE INITIAL CONDITIONS MAINTAINED? CHANNELS?
 POTENTIALLY SIGNIFICANT SURFACE
EFFECTS IN (LIQUID) ABSORPTION

 Adsorption (How well do HSP match?)

 Polymer rotation to match HSP of external
phase: reason for success with a constant h?
 Orientation (Does n-hexane enter sideways?)
 Absorption site (hole size and shape)
 Number of absorption sites (Equilibrium
uptake and similarity of HSP)
 Transport into bulk (Diffusion coefficient,
molecular size and shape)
 CONCLUSION:
STRESS RELAXATION NEED NOT BE INVOKED.
Exclusively bulk phenomena such as stress
relaxation or swelling stress need not be
invoked to explain the cases examined
including Thomas and Windle Case II, Super
Case II, and Sigmoidal examples, or the
studies of Petropoulos and coworkers.
The diffusion equation can fully describe all of
these studies and those of Hansen when the
a significant surface condition is included and
exponential diffusion coefficients are used.
 SUMMARY
 Laws of Diffusion are Valid
 Exponential Diffusion Coefficients
 Surface Condition involved with ”Anomalies”
 Combine These - No Anomalies
 Exclusively Bulk Explanations not possible
 Estimate Behavior at Different Conditions
 Improved understanding and modeling of
absorption, desorption, and permeation
 Improve Barriers with (HSPp ≠ ≠ HSPs)
Thank you for your attention!

For further contact please visit:

www.hansen-solubility.com
 PERMEATION WITH SURFACE
AND/OR EXTERNAL RESISTANCES

F = p/(L/Papp) = p/(L/P + R1 + R2 + R3 …)

L/Papp = L/P + R1 + R2 + R3 ….

1/Papp = 1/P + (R1 + R2 + R3 ….)/L

Use Plot of 1/P Versus 1/L

TRUE PERMEATION COEFFICIENT (P∞)
BY EXTRAPOLATION (ACRYLIC FILMS)
1 x 10-12
Papp

20

15

10

P
5

1 x 10-3
0 5 10 15 20 25 L
 DIFFUSION SIDE EFFECTS

 Film: Thickness (L), length (l), width (w)

D0 = Dapp /(1 + L/l + L/w)2

 Circular Film: Thickness (b), Radius (R)

D0 = Dapp/(1 + b/R)2

 For L = 1mm and w = 10mm: Dapp/D0 = 1.21

 Tensile bars (L = 2-4mm, w=10mm): Do not use!

CASE II ABSORPTION WITH LINEAR UPTAKE
WITH LINEAR TIME. THE SURFACE
CONCENTRATION INCREASES SLOWLY
 SUPER CASE II WITH SLOWLY INCREASING
RATE OF ABSORPTION WITH TIME.
CONCENTRATION GRADIENTS SHOW A FRONT.
WHOLE EQUALS SUM OF PARTS
E = COHESION ENERGY = ΔEvap
 E = E D + E P + EH
 D - Dispersion (Hydrocarbon)
 P - Polar (Dipolar)
 H - Hydrogen Bonds (Electron Interchange)
 V - Molar Volume
 E/V = ED/V + EP/V + EH/V
2 2 2 2
 =  D +  P +  H
HANSEN SOLUBILITY PARAMETERS (HSP)
 = Square Root of Cohesion Energy Density
 KEY EQUATIONS

Ra = 4(D1 - D2) + (P1 - P2) + (H1 - H2)

2 2 2 2


 The experimentally verified ”4” is also found in

Prigogine’s CST theory

 RED = Ra/Ro (Distance to sphere center divided

by its radius)

2 2
 (RED) = (Ra/Ro) corresponds to  / in
12 c
Huggins/Flory Theory
 FREE ENERGY CHANGE, G,
DETERMINES SOLUBILITY OR NOT
 Free energy G must be negative for solution

 G = (1/N)øln(ø) + (1 - ø)ln(1 - ø) + Χø(1 - ø)

 ø is the solvent volume fraction

 N is the number of monomers in chain

 Χ = Vm/RT[(D1 - D2)2 + 0.25(P1 - P2)2 +

0.25(H1 - H2)2 ]

 Χ is the chi parameter, Vm is the molar volume